Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

Kourkine, Igor V.; Glueck, David S.

doi:10.1021/ic970730g

Cited by 37 publications

(29 citation statements)

References 30 publications

(44 reference statements)

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“…Glueck and Kourkine prepared the neutral diplatinum complex 30 upon deprotonation of the dicationic complex [Pt 2 (μ-PHMes) 2 (dppe) 2 ] 2+ (dppe = Ph 2 PCH 2 CH 2 PPh 2 ) with a two-fold excess of n BuLi (Scheme 15) [41]. The singly-deprotonated compound 31 was also accessible either by using 1 equivalent of base or, alternatively, by addition of HBF 4 to 30.…”

Section: Scheme 14mentioning

confidence: 99%

“…All these complexes have Sc-P bond lengths in the range 2. 41 Significant structural data are also available for an extensive family of dinuclear tantalum complexes reported by the groups of Hey-Hawkins [30,44] and Fryzuk [46]. All these complexes display trigonal planar geometry around the P atoms, with relatively short Ta-P lengths (av.…”

Section: Symmetric Trigonal Planar Phosphinidene Complexesmentioning

confidence: 99%

“…Likewise, the diplatinum phosphinidene complex 30, also generated in situ, reacted with excess MeI to form the phosphanyl dication 76, whereas the addition of excess BH 3 ·THF led to the borane adduct 77 (Scheme 41) [41].…”

Section: Reactions With Simple Electrophilesmentioning

confidence: 99%

“…Oxidation of the diplatinum complex 30 with air or O 2 gives one of the possible isomers of the bis(phosphinidene oxide) complex 95, which could be only characterised by NMR, since attempts to crystallise it led to its decomposition (Scheme 52) [41]. A related sulphide analogue was expected in the reaction with sulphur, but instead the trithiophosphorane complex 96 was obtained.…”

Section: Oxidation Reactions With Group 16 Elements and Related Procementioning

confidence: 99%

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Phosphinidene-bridged binuclear complexes

Garcı́a

García‐Vivó

Ramos

et al. 2017

Coordination Chemistry Reviews

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This article contains a comprehensive review of the work carried out within the last three decades on the synthesis, structural studies and reactivity of the binuclear complexes of transition and lanthanide elements bearing bridging phosphinidene (PR) ligands. The latter are grouped into three different classes according to their geometry and electronic distribution: pyramidal, symmetric planar trigonal and asymmetric planar trigonal. Different reactivity patterns can be then outlined for each of these classes of metal complexes, which differ in many ways from those characterizing the extensively studied chemical behaviour of mononuclear phosphinidene complexes.

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Section: Scheme 14mentioning

confidence: 99%

Section: Symmetric Trigonal Planar Phosphinidene Complexesmentioning

confidence: 99%

Section: Reactions With Simple Electrophilesmentioning

confidence: 99%

Section: Oxidation Reactions With Group 16 Elements and Related Procementioning

confidence: 99%

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Phosphinidene-bridged binuclear complexes

Garcı́a

García‐Vivó

Ramos

et al. 2017

Coordination Chemistry Reviews

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“…Indeed, terminal phosphinidene ligands involving nickel have exhibited interesting reaction chemistry [10,21,22], suggestive of high potential reactivity at platinum. However, similar to imido ligands, only a l-phosphinidene compound is known, reported by Glueck [23].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structure, and reactivity of platinum compounds featuring terminal amido and phosphido ligands

Waterman¹,

Mindiola²,

Clough³

et al. 2014

Inorganica Chimica Acta

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Ruthenium‐Stabilized Low‐Coordinate Phosphorus Atoms: Structural Evidence for Monomeric Metaphosphonate

et al. 2003

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The metaphosphate anion has attracted steady interest since 1955 [1] in connection with wide applications in phosphorylation reactions.[2] It has relevance in biochemistry in particular with respect to ATP hydrolysis.[3] However, despite considerable efforts, monomeric metaphosphates and other dioxophosphoranes are only known as transient species in solution and their existence can be inferred from trapping experiments. [2][3][4] Their high reactivity arises from the powerful electrophilic character at the phosphorus center. Several approaches have been tested to stabilize these highly reactive species. Kinetic stabilization by steric protection [5] proved to be ineffective for dioxophosphorane and led to products that resulted from the insertion of the PO 2 moiety in a neighboring group.[6] The electrophilicity and the tendency to expand the valence shell were exploited for their stabilization as Lewis salts. This strategy allowed only spectroscopic characterization by 31 P NMR in a few cases. [7] Thus, the chemistry of dioxophosphorane suffers from a paucity of information and new approaches to stabilize and enable deeper investigation are highly desirable. This work describes the first isolation and full characterization, including X-ray structural analysis, of stabilized metaphosphonate.We have developed a novel and successful route to ruthenium-stabilized monomeric metaphosphonate by oxidation of a nucleophilic terminal phosphinidene complex of ruthenium. As recently described by Lammerstma and coworkers, the terminal phosphinidene ruthenium complexes [(h 6 -p-cymene)Ru(PR 3 )(PMes*)] (3 a: R = Cy, 3 b: R = Ph [8] ) are formed as dark green solids by the reaction of the primary phosphane complex [(h 6 -p-cymene)RuCl 2 (PH 2 Mes*)](1; pcymene = 4-methyl-iso-propylbenzene; Mes* = 2,4,6-tri-tertbutylphenyl) with two equivalents of 1,8-diazabicyclo[5-4-0]undec-7-ene (DBU) in the presence of PR 3 as a stabilizing ligand (R = Ph, Cy).[8] Alternatively, treatment of [(h 6 -pcymene)RuCl 2 (PR 3 )] (2 a: R = Cy, 2 b: R = Ph) and PH 2 Mes* with DBU affords 3 in high yields (Scheme 1).

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Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

Cited by 37 publications

References 30 publications

Phosphinidene-bridged binuclear complexes

Phosphinidene-bridged binuclear complexes

Synthesis, structure, and reactivity of platinum compounds featuring terminal amido and phosphido ligands

Ruthenium‐Stabilized Low‐Coordinate Phosphorus Atoms: Structural Evidence for Monomeric Metaphosphonate

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